Exterior deep base paint formulation

ABSTRACT

The present invention provides increased stain resistance, tannin blocking, adhesion, and various other properties. A composition in accordance with the principles of the present invention comprises at least three binders, nanoparticle pigment, and pigmentary titanium dioxide. In one embodiment, the present invention relates to a coating on a substrate wherein the coating has three binders, nanoparticle metal oxide pigment, and pigmentary titanium dioxide. Various additives may be included to formulate paint as known in the art.

RELATED APPLICATIONS

This application is a continuation-in-part of U.S. patent application Ser. No. 10/914,439, hereby incorporated in its entirety.

FIELD OF THE INVENTION

The present invention relates to paints with polymer resin deep base formulation. More particularly, the present invention relates to paints having a nanoparticle based pigment and at least three binders.

BACKGROUND OF THE INVENTION

Traditionally, consumers have had to choose between the superior durability offered by latex paints and the superior hiding properties of oil-based paint. Conventional latex or emulsion paints require an underlying primer coat prior to their application to provide an adequate level of blocking and to prevent bleed-through, such as of tannins. In addition, many conventional latex paints require a primer coat to provide adequate adhesion and durability for specific applications. Often, even when a primer is applied, multiple coats of the prior art paints are required to prevent an alteration of color due to the presence of the primer or bleed through of dyes and pigments from the underlying substrate. In fact, multiple applications of prior art paint will not prevent bleed-through on substrates such as cedar since the dyes and pigments, such as tannins contained in the substrates, are often water soluble and diffuse through each layer of the latex paint.

Paint typically contains four essential ingredients, namely pigment, binder, liquid and additives. Any or all of these ingredients may be a single component or may comprise multiple items. Pigment provides color to paint and also makes paint opaque, and pigment is usually of mineral or organic origin although some pigments are artificially produced. Some pigments possess little or no bulk and must be fixed on a more solid, but at the same time transparent, substance or base. “Prime” pigments provide color and opacity (opaque coverage). The most common prime pigment is titanium dioxide, which is white and is used in latex and oil-based paints.

Traditionally, pigments have also added hiding properties to paint. Specialty or extender pigments may also be used and provide bulk to the paint at a low cost. The extender pigments are often chosen for their impact on properties like scrub resistance, stain resistance and chalk resistance. Alum or clay are frequently used for this purpose. These pigments are added to the paint to provide certain characteristics such as thickness, a certain level of gloss and durability. They are usually naturally occurring products which originally were in the earth and were mined and purified for use in paint. Such pigments as calcium carbonate, talc and clay are, for example, used extensively in paints.

The binder holds the pigment and also adheres it to a surface, and a binder composition may have more than one component. In latex paint, the latex resin is the binder. Most commonly in latex paint, the binder is 100% acrylic, vinyl acrylic (polyvinyl acetate), or styrenated acrylic. The pigment particles are insoluble and merely form a suspension in the binder. The binder “binds” the pigment into a tough, continuous film and as noted above helps the paint adhere to the surface. In addition, it has been found previously that the use of 100% acrylic binder provides for maximum adhesion when wet and also provides for resistance to blistering and peeling, resistance to mildew and dirt, and alkali resistance for paint applied over fresh masonry.

Liquids carry the pigment and binders, and this liquid is the part of the paint or coatings product which evaporates. The role of the liquid is to keep the paint in a fluid form for ease of application. Once applied to the surface it evaporates leaving a uniform film which then dries to form a protective coating. The liquid used is primarily determined by the solubility of the binder. In oil-based and alkyd paints, the liquid is typically an organic solvent, and in latex paints, the liquid is typically water. Traditionally, top quality paints have less liquid and more solids (i.e. pigment & binders) as measured by percent solid.

Additives are ingredients used at low levels to provide key properties, such as but not limited to: mildew resistance, improved flow and leveling, and spatter resistance. Common additives used in conventional paint formulations include rheology modifiers, surfactants, defoamers, coalescents, and biocides. Other numerous additives are well-known in the art and may be utilized as required to formulate a paint having the desired properties.

Various techniques are known in the art for producing paints having various types of sheens, i.e. “shine” or gloss. For example, by incrementally increasing pigment levels and/or by using larger pigment particles, various gloss levels can be achieved including, but not limited to flat, satin, and semi-gloss. Pigment volume concentration (PVC) is often associated with the paint finish, although various finishes may have overlapping ranges of PVC. PVC is the unit volume of pigments as a percentage of the volume of pigments plus the volume of the binder. PVC represents the relationship between durability of the coating and the amount of pigment.

In addition to the sheens, it is well known in the art to formulate paint compositions to allow for the desired pigment which is added for color. For example, where a near white coating is desired a high volume of TiO₂ may be used and a small volume of coloring pigment is necessary. In contrast, where a dark color is preferred in the final coating, a large volume of coloring pigment is needed and a corresponding decrease in the amount of TiO₂ is necessary.

Thus, there is a need for a high colorant volume paint composition and method of making the same to replace the traditional role of a primer and topcoat system and which is capable of providing a coating having improved properties such as, tannin blocking, hiding power, stain removal, and corrosion resistance.

SUMMARY OF THE INVENTION

The present invention relates generally to a binder composition and a paint system with superior tannin blocking, stain removal, corrosion resistance, adhesion, and various other improved properties. The present invention preferably includes a three binder system with an inorganic nano-particle pigment and with a pigmentary titanium dioxide. In one embodiment, a paint composition in accordance with the principles of the present invention further includes additives for formulating paint. In another embodiment, the present invention relates to a coating on a substrate that provides improved coverage through the use of at least three binders, an inorganic nano-particle pigment and a pigmentary titanium dioxide.

BRIEF DESCRIPTION OF THE DRAWINGS

FIG. 1 depicts a multi-axis property graph of the test results of paint of the present invention having a satin sheen and white base, as compared to commercially available exterior satin in a white base;

FIG. 2 depicts a multi-axis property graph of the test results of flat white base paint in accordance with the principles of the present invention, as compared to a commercially available exterior flat paint in a white base;

FIG. 3 illustrates a multi-axis property graph of the test results for semi-gloss white base paint of the present invention versus a commercially-available, exterior semi-gloss paint in a white base;

FIG. 4 illustrates a multi-axis property graph for a flat white base paint of the present invention versus a second commercially available exterior flat paint in a white base;

FIG. 5 illustrates a multi-axis property graph for a satin white base paint of the present invention versus a second commercially-available, exterior satin paint in a white base;

FIG. 6 illustrates a multi-axis property graph for a semigloss deep base paint of the present invention versus a commercially-available exterior paint; and

FIG. 7 illustrates a multi-axis property graph for a satin deep base paint of the present invention versus a commercially-available exterior paint.

DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

The present invention is directed in part to a polymer composition within a paint system which replaces the traditional role of a primer and a topcoat with improved properties such as tannin blocking, stain removal, adhesion, and corrosion resistance. In one embodiment, the present invention relates to a composition having a first binder, a second binder, inorganic nanoparticle pigments, and in some cases a third binder. This composition can be used in a conventional paint formulation as known in the art.

Binders for use in the present invention include those prepared by conventionally known methods. Suitable binders include, but are not limited to, 100% acrylic resins and styrenated, acrylic resins as manufactured. Preferably, the first binder is a 100% acrylic resin designed to be used as a primer vehicle, and the second binder is a 100% acrylic resin designed to be used in top coating applications.

Pigments for use in the present invention may comprise any suitable pigments known in the art. In one embodiment, the pigments of the present invention are titanium oxide or zinc oxide but other suitable pigments include nepheline syenite, bentonite, and calcium carbonate. Preferably, the primary pigment is titanium dioxide, such as commercially available pigments.

Metal oxide nanoparticle materials for use in a preferred embodiment of the invention have an average particle size of about 20-150 nanometers, although some embodiments can employ average sizes outside this range. In one preferred embodiment, the nanoparticle material is a zinc oxide material having an average particle size of about 60 nm.

A paint can be prepared in accordance with the principles of the present invention according to a number of known manufacturing methods. Generally, such methods involve the preparation of a binder or a multiple binder system, mixing of the additional ingredients, dispersing of the pigments, and adjusting the density and viscosity to desired levels. A variety of additives and diluents which are well known in the art can be mixed with the binders of the present invention to achieve certain properties in the paint or the coating. The additives may include, but are not limited to, surfactants, defoamers, rheology modifiers, coalescents, biocides, mildewcides, surfactants, and other additives well known in the art.

In one embodiment, a paint in accordance with the principles of the present invention is manufactured to a VOC (Volatile Organic Compounds) content of about 150 grams per liter (gr/L), including about 37% solid by volume, about 51% solid by weight, about 34 PVC, and about 1.5 pigment to binder ratio.

The PVC of paint in accordance with the principles of a preferred form of the present invention may vary between about 4 and about 55 by weight. In one embodiment of the present invention the paint is a “semi-gloss paint”, which has a relatively low PVC. In another embodiment of the present invention, the paint is a “satin paint”, which has a relatively high PVC. In another embodiment of the present invention, the paint is a “flat paint”, which has a relatively high PVC compared to satin paint.

Table 1 lists the general ranges of the main ingredients of a paint in accordance with the principles of a preferred embodiment. The total amount of binder (i.e., polymer, latex, vehicle) is preferably between about 30 and about 60 gallons per 100 gallons. The total amount of pigment, excluding the titanium dioxide (TiO₂), is preferably between about 15 and about 325 pounds per 100 gallons. The TiO₂ content is preferably between 0 pounds per gallon and about 360 pounds per 100 gallons. The preservatives comprise between about 5 and about 8 pounds per 100 gallons. Additional additives comprise about 50 and about 200 pounds per 100 gallons. Water comprises between about 50 and about 200 pounds per 100 gallons. The paint further includes additional solvent, aside from the water content of between about 0 and about 45 pounds per 100 gallons.

TABLE 1 Ingredients Range Pounds/100 Gallons Category Minimum Maximum Additive 50.00 200.00 Binder 450.00 635.00 Extender Pigment 15.00 150.0 Titanium Dioxide 0.00 360.00 Preservative 5.0 8.0 Water 50.00 200.00 Solvent 0.00 45.00 Total 600 1598 Volume % Solids 25 40 Weight % Solids 30 55 PVC 4 55

The preferred formulation process consists of two conventional steps: the grind and the letdown. During the grind, the solvent (water), dispersant, defoamer, zinc oxide, ethylene glycol, amino alcohol, nepheline syenite, attapulgite clay are mixed together. During the letdown, the binder, the mildewcide, the rheology modifier, and the biocide, are added to the grind product.

The following non-limiting examples illustrate main components of the paint formulations and the paint formulations themselves. Table 2 provides the material ranges for the components of the paint formulations of Examples 1-4.

TABLE 2 Raw Material Ranges Range in Raw Material lbs/100 gal Water  70–220 Copolymer Dispersant 10–20 Nanoparticle Inorganic Oxide  4–20 Zinc Oxide 0–7 Phosphated Co-Ester Surfactant 3–6 Mineral Oil Defoamer 4–8 Extender Pigment  10–305 Glycol  0–35 Rheology Modifier 15–30 100% Acrylic Primer Binder 340–430 100% Acrylic Topcoat Binder  70–100 Styrene Acrylic Topcoat Binder  0–180 Coalescent  0–15 In-can Biocide 0.5–2   Mildewcide 6–8 Non-ionic Rheology Modifier  7–25 Amino Alcohol 0–1 Titanium Dioxide  0–350 Bentonite 0–6 Fluoro Surfactant   0–0.4 Opaque Polymer  0–110 Attapulgite Clay 0–8 Non-ionic Surfactant 0–5 Calcined Diatomaceous  0–45

EXAMPLE 1 Semi-Gloss Finish

Example 1 was formulated using the basic components of Table 2, with the following specific components:

TABLE 3 Description Amount Weight % Grind Water 73.92 6.98 Copolymer Dispersant 15.02 1.42 Mineral Oil Defoamer 2.00 0.19 Zinc Oxide 5.00 0.47 Nanoparticle Metal Oxide 3.00 0.28 Ethylene Glycol 32.00 3.02 Amino Alcohol 0.50 0.05 Non-ionic Surfactant 4.00 0.38 Nepheline Syenite 10.00 0.94 Attapulgite Clay 5.00 0.47 Letdown 100% Acrylic Primer Binder 410.65 38.77 100% Acrylic Topcoat Binder 86.44 8.16 Mineral Oil Defoamer 3.00 0.28 TiO₂ Slurry 297.00 28.04 Coalescent 8.00 0.76 Associative Rheology Modifier 28.00 2.64 Non-ionic HEUR Rheology 8.00 0.76 Modifier Opaque Polymer 58.80 5.55 Phosphated Co-ester Surfactant 1.00 0.09 Mildewcide 6.94 0.65 In-can Biocide 1.00 0.09

EXAMPLE 2 Satin Finish

Example 2 was formulated using the basic components of Table 2, with the following specific components:

TABLE 4 Grind Amount Weight % Water 45.35 4.06 Copolymer Dispersant 15.02 1.35 Mineral Oil Defoamer 3.00 0.27 Nanoparticle Metal Oxide 15.00 1.34 Ethylene Glycol 37.00 3.32 Amino Alcohol 0.50 0.04 Non-ionic Surfactant 2.00 0.18 Nepheline Syenite 105.02 9.41 Attapulgite Clay 5.01 0.45 Letdown 100% Acrylic Primer Binder 410.60 36.82 100% Acrylic Topcoat Binder 86.43 7.75 TiO₂ Slurry 294.32 26.39 Coalescent 8.00 0.72 Phosphated Co-ester Surfactant 1.00 0.09 Associative Rheology Modifier 25.00 2.24 Non-ionic HEUR Rheology 4.00 0.36 Modifier Opaque Polymer 50.05 4.49 Mildewcide 6.94 0.62 In-can Biocide 1.00 0.09

EXAMPLE 3 Flat Finish

Example 3 was formulated using the basic components of Table 2, with the following specific components:

TABLE 5 Grind Amount Weight % Water 25.27 2.18 Ethylene Glycol 22.55 1.95 Non-ionic Surfactant 2.00 0.17 Copolymer Dispersant 15.30 1.32 Zinc Oxide 4.92 0.42 Nanoparticle Metal Oxide 4.92 0.43 Amino Alcohol 0.98 0.09 Mineral Oil Defoamer 1.97 0.17 Nepheline Syenite 94.70 8.18 Attapulgite Clay 7.92 0.68 Phosphated Co-ester Surfactant 3.87 0.33 Letdown TiO₂ Slurry 350.02 30.26 Water 82.22 7.1 Calcined Diatomaceous Earth 44.28 3.82 100% Acrylic Primer Binder 285.04 24.64 100% Acrylic Topcoat Binder 60.02 5.19 Opaque Polymer 105.79 9.15 Coalescent 7.87 0.68 Associative Rheology Modifier 18.81 1.63 Mildewcide 6.82 0.59 Mineral Oil Defoamer 3.94 0.34 Non-ionic HEUR Rheology 6.43 0.56 Modifier In-can Biocide 0.96 0.08

EXAMPLE 4 Flat Finish

Example 4 was formulated using the basic components of Table 2, with the following specific components:

TABLE 6 Grind Amount Weight % Water 197.00 21.15 Ethylene Glycol 30.00 3.22 Non-ionic Surfactant 1.00 0.85 Copolymer Dispersant 8.00 0.86 Nanoparticle Metal Oxide 8.00 0.86 Mineral Oil Defoamer 6.00 0.64 Nepheline Syenite 90.0 9.64 Bentonite 6.00 0.64 Letdown Opaque 4.00 .43 100% Acrylic Primer Binder 366.00 39.3 100% Acrylic First Topcoat Binder 77.00 8.27 Second Acrylic Topcoat Binder 82.00 8.8 Coalescent 5.00 0.54 Associative Rheology Modifier 18.00 1.9 Mildewcide 6.92 0.74 Non-ionic HEUR Rheology 25.00 2.68 Modifier In-can Biocide 1.00 0.1

Adhesion Tests

Various adhesion tests were performed to determine the adhesion properties of a paint in accordance with the principles of the present invention on different substances. The results of the tests compare a paint of the present invention to a typical, commercially-available paint and typical, commercially available primer, and these tests are presented in Table 7.

TABLE 7 Adhesion Test Results Rated by ASTM D3359 Acrylic Exterior Satin Paint Formulation Acrylic Exterior Primer* Satin Topcoat* Adhesion Test Test Condition of the present invention (Control) (Control) Alkyd green overnight, dry/wet 5B/4B 5B/4B 5B/5B gray overnight, dry/wet 5B/5B 5B/5B 5B/5B Chalk blue latex panel overnight, dry/wet 5B/5B 5B/4B 5B/5B Wood Cedar overnight, dry/wet 4B/5B 3B/3B 4B/5B Oak overnight, dry/wet 5B/5B 5B/4B 5B/5B Redwood overnight, dry/wet 5B/5B 5B/4B 5B/5B PT green overnight, dry/wet 5B/5B 5B/5B 5B/5B Vinyl Siding new vinyl overnight, dry/wet 5B/5B 5B/5B B/5B weathered vinyl overnight, dry/wet 5B/5B 5B/5B 5B/5B Metals galvanized steel overnight, dry/wet 4B/5B 3B/3B 0B/0B 3 day, dry/wet 5B/3B 4B/4B 0B/0B aluminum roll overnight, dry/wet 2B/3B 3B/3B 0B/0B 3 day, dry/wet 4B/5B 4B/4B 0B/0B Miscellaneous glossy black tile overnight, dry/wet 5B/3B 2B/0B 0B/0B 3 day, dry/wet 5B/5B 5B/2B 0B/0B clay tile overnight, dry/wet 5B/3B 1B/0B 1B/0B 3 day, dry/wet 5B/5B 5B/5B 3B/0B bull nose brick overnight, dry/wet 5B/0B 4B/0B 4B/0B 3 day, dry/wet 5B/0B 5B/0B 2B/0B *The control Acrylic Exterior Primer and Control Acrylic Exterior Topcoat tested were at least comparable to those readily available on the commercial market.

In addition, a battery of tests were performed to evaluate the overall performance of a paint in accordance with the principles of the present invention at various sheens as compared to paints currently available in the marketplace. As shown in the results in Tables 8 and 9, the paint prepared in accordance with the principles of the present invention outperformed all of the other paints in the respective category.

TABLE 8 Flat Sheen Benchmarking Composite Scores Flat Paint Formulation of the Present Commercial Acrylic Test Invention Flat** Possible Score Freeze-Thaw 1 0 2 Heat Stability 1.5 3 3 Applied Holding 7.5 5 10 Leveling 5 0 5 Touch-up 7.5 10 10 Drying Time 2 2 2 Sag Resistance 3 3 3 Roller Foam 3 3 3 Roller Spatter 1 0.5 1 3 mil Contrast 20 6 20 Ratio Dry Adhesion 12 7.5 15 Blistering 9 9 9 Resistance Wet Adhesion 15 15 15 Water Spotting 2 2 2 Total Score 89.5 66 100 **The Commercial Acrylic Flat paint tested was at least comparable to those readily available on the commercial market.

As seen in Table 9, the satin sheen of the present invention exhibits improved leveling, roller foam, contrast, and dry adhesion.

TABLE 9 Satin Sheen Benchmarking Composite Scores Satin Paint Formulation of Commercial the Present Commercial Acrylic Silicone Acrylic Test Invention Exterior Satin*** Exterior Satin*** Possible Score Freeze-Thaw 2 1 2 2 Heat Stability 3 3 3 3 Applied Holding 10 5 10 10 Leveling 5 2.5 0 5 Touch-up 7.5 4 7.5 10 Drying Time 2 2 2 2 Sag Resistance 3 3 3 3 Roller Foam 3 3 1.5 3 Roller Spatter 1 1 1 1 3 mil Contrast 20 20 14 20 Ratio Dry Adhesion 12 0 12 15 Blistering 15 7 15 9 Resistance Wet Adhesion 9 15 9 15 Water Spotting 2 2 2 2 Total Score 94.5 68.5 82 100 ***The Commercial Acrylic Satin Exterior and Commercial Silicone Acrylic Exterior Satin tested were at least comparable to those readily available on the commercial market.

As illustrated in FIGS. 1, 2, 3, 4, and 5, paint prepared in accordance with the principles of the present invention exhibits improvements in adhesion, tannin blocking, stain removal, hiding power, and corrosion resistance. FIG. 1 depicts a multi-axis property graph of the test results of paint of the present invention having a satin sheen and white base, as compared to commercially-available, exterior satin in a white base. Adhesion, yellowing, stain removal, hiding power, scrub resistance, corrosion, and tannin blocking were measured. FIG. 2 depicts a multi-axis property graph of the test results of flat white base paint in accordance with the principles of the present invention, as compared to a commercially available exterior flat paint in a white base. FIG. 3 illustrates a multi-axis property graph of the test results for semi-gloss white base paint of the present invention versus a commercially available exterior semi-gloss paint in a white base. All properties were improved in formulations in accordance with the principles of the present invention with the exception of scrub resistance and yellowing, which showed a reduction. FIG. 4 illustrates a multi-axis property graph for a flat white base paint of the present invention versus a second commercially-available, exterior flat paint in a white base. All properties were improved in formulations in accordance with the principles of the present invention. FIG. 5 illustrates a multi-axis property graph for a satin white base paint of the present invention verses a second commercially-available, exterior satin paint in a white base. All properties were improved in formulations in accordance with the principles of the present invention.

Deep Base Formulations

One aspect of the present invention relates to paints which have deep base formulations. Deep base formulations are generally understood by the art as base paint formulations which are intended to have a high level of pigment added to them to achieve the desired color, typically a very vivid or dark color. The present invention shall refer to any of the multitude of formulations designed to accept larger volumes of pigment as “deep base”, though such formulations are sometimes refers to not only as deep base, but as accent base, ultra-deep base, and neutral base. These formulations are designed to be able to accept a larger volume (and weight percent) of pigment. In one embodiment, paint formulations which include less than 60 pounds/100 gallons of pigmentary-sized pigment (e.g. TiO₂) are considered to be deep base formulations.

In one embodiment, in a deep base formulation, the three binder system previously described exhibits less than ideal characteristics when dried. Thus, in one exemplary embodiment of the present invention, a third binder is added to the paint formulation to form a composition which exhibits the properties of “lighter” base paints as discussed previously and shown in FIGS. 1-5. This third binder comprises a second topcoat binder. Thus, a deep base formulation in accordance with the principles of the present invention comprises a first primer binder, a first topcoat binder, and a second topcoat binder. In one embodiment, the binders are acrylic binders; and in one exemplary embodiment, the binders are each self-crosslinking. In one embodiment, the amount of the second topcoat binder is varied in relation to the amount of TiO₂ to be added (i.e., less TiO₂ is utilized when more colorant is used). Table 10 provides a general formulation for a deep base paint in accordance with the principles of the present invention. Such deep base formulations can be designed, as known in the art, to have any of the paint coating finishes discussed above, such as semi gloss or satin. In addition, one of ordinary skill in the art will appreciate that the ratio of primer to topcoat binder maybe be varied to achieve the desired balance of coverage (primer) and finished look (topcoat).

TABLE 10 General Deep Base Formulation Approximate Solid Grind Weight % Water  4–20 Ethylene Glycol 2.0–2.5 Copolymer Dispersant 0.5–1.0 Nanoparticle Metal Oxide 0.5–1.0 Mineral Oil Defoamer   0–0.5 Nepheline Syenite 1.5–2.5 Clay 0.2–0.3 Nonionic surfactant 0.3–0.5 Letdown Cellulosic thickener   0–0.2 Water 0–5 First Primer Binder 10–22 First Topcoat Binder 2–6 Second Topcoat Binder 35–55 Coalescent 2–3 Rheology Modifier 0.5–1.0 Mildewcide   0–1.0 Non-ionic HEUR Rheology 3–5 Modifier In-can Biocide   0–0.2

Deep Base Examples

FIGS. 6 and 7 depict a multi-axis property graphs of the test results, similar to those in FIGS. 1-5 for the two-binder formulation described above, of a deep base paint of Table 11, as compared to commercially-available, exterior paint. FIG. 6 provides a comparison of a semigloss deep base paint having a 70/30 ratio as set forth in Table 11. FIG. 7 provides a similar comparison as FIG. 6, but for a 70/30 ratio deep base having a satin finish as listed in Table 12.

As discussed above, the present invention encompasses various ratios of the three binders depending on the desired “finish” of the coating. Table 11 illustrates the same information for a semigloss finish. Table 12 illustrates exemplary weight percentages and ratios for three common binder ratios for a satin finish.

TABLE 11 Weight Ratios for semigloss “Deep Base” formulations Semigloss Deep Wet lbs Dry lbs % by dry weight solid Ratio 60:40 Ratio First primer binder 193 83 31 40 First topcoat binder 49 25 9 Second topcoat binder 356 160 60 60 70:30 Ratio First primer binder 145 62 23 30 First topcoat binder 37 19 7 Second topcoat binder 416 187 70 70 80:20 Ratio First primer binder 97 41 15.5 20 First topcoat binder 25 13 4.5 Second topcoat binder 476 214 80 80

TABLE 12 Weight Ratios for satin “Deep Base” formulations Satin Deep Wet lbs Dry lbs % by dry weight solid Ratio 60:40 Ratio First primer binder 192 83 31 40 First topcoat binder 48 25 9 Second topcoat binder 355 160 60 60 70:30 Ratio First primer binder 144 62 23 30 First topcoat binder 36 19 7 Second topcoat binder 415 187 70 70 80:20 Ratio First primer binder 96 41 15.5 20 First topcoat binder 24 12 4.5 Second topcoat binder 475 214 80 80

While several embodiments have been shown and described in this application, it is understood that changes and modifications can be made to the invention without departing from the invention's broader aspects. The examples and specific formulations are for illustrative purposes and should not be construed as limiting the scope of the invention. Unless otherwise specified, weight percentages are solid weight percentages. 

1. A paint composition comprising: a first primer binder of about 10 weight percent to about 22 weight percent; a first topcoat binder of about 2 weight percent to about 6 weight percent; a second topcoat binder from about 35 weight percent to about 55 weight percent; and a nanoparticle-sized metal oxide pigment of about 0.5 weight percent to about 1 weight percent.
 2. The composition of claim 1, wherein the nanoparticle metal oxide pigment comprises zinc oxide.
 3. The composition of claim 1, wherein the nanoparticle metal oxide pigment comprises particles having an average particle size of less than about 100 nanometers.
 4. The composition of claim 3, wherein the nanoparticle metal oxide pigment comprises particles having an average particle size of between about 30 nanometers and about 65 nanometers.
 5. The composition of claim 1, wherein the first primer binder consists essentially of acrylic.
 6. The composition of claim 1, wherein the first topcoat binder consists essentially of acrylic.
 7. The composition of claim 1, wherein the first primer binder comprises self-crosslinking polymer.
 8. The composition of claim 1, wherein the first primer binder comprises a 100% acrylic binder as a primer vehicle.
 9. The composition of claim 1, wherein the ratio of the first primer binder and the first topcoat binder to the second topcoat binder is about 4:1.
 10. The composition of claim 1 wherein the ratio of the first primer binder and the first topcoat binder to the second topcoat binder is about 7:3.
 11. The composition of claim 1, wherein the ratio of the first primer binder and the first topcoat binder to the second topcoat binder is about 3:2.
 12. A process for producing a paint composition comprising the steps of: dispersing a pigment in a solvent to form a dispersion; mixing the dispersion with grind additives comprising a nanoparticle metal oxide; adding a first primer binder, a first topcoat acrylic binder, and a second topcoat acrylic binder to the dispersion; and adding letdown additives to the dispersion.
 13. The process of claim 12, wherein the nanoparticle metal oxide comprises zinc oxide.
 14. The process of claim 12, wherein the nanoparticle metal oxide comprises particles having an average particle size of less than 100 nanometers.
 15. The process of claim 12, wherein the nanoparticle metal oxide comprises particles having an average particle size of between about 30 nanometers and about 65 nanometers.
 16. The process of claim 12, wherein the step of adding the first primer binder includes adding a 100% acrylic binder.
 17. The composition of claim 12, wherein the step of adding the first topcoat acrylic binder includes adding a 100% acrylic binder.
 18. The composition of claim 12, wherein the first acrylic primer binder comprises a self-crosslinking polymer.
 19. The composition of claim 12, wherein the second primer binder comprises a 100% acrylic binder.
 20. The composition of claim 12, wherein the ratio of first primer binder and the first topcoat binder to the second topcoat binder is about 80:20.
 21. A coated substrate comprising: a substrate; and a coating on the substrate having: a first binder, a second binder, and a third binder; a pigmentary-sized pigment; and a nanoparticle-sized metal oxide.
 22. The coated substrate of claim 21, wherein the nanoparticle metal oxide comprises zinc oxide.
 23. The coated substrate of claim 21, wherein the nanoparticle metal oxide comprises particles having an average particle size of less than 100 nanometers.
 24. The coated substrate of claim 21, wherein the nanoparticle metal oxide comprises particles having an average particle size of between about 30 nanometers and about 65 nanometers.
 25. The coated substrate of claim 21, wherein the first binder comprises a 100% acrylic primer binder.
 26. The coated substrate of claim 21, wherein the second binder comprises a 100% acrylic topcoat binder.
 27. The coated substrate of claim 21, wherein the third binder comprises a 100% acrylic topcoat binder.
 28. The coated substrate of claim 21, wherein the first binder, the second binder, and the third binder, comprise self-crosslinking polymers.
 29. The coated substrate of claim 21, wherein the ratio of first primer binder and the first topcoat binder to the second topcoat binder is between about 4:1 to about 3:2.
 30. The coated substrate of claim 21, wherein the the first binder has a weight percent of about 10.5 to about 22.0; a second binder has a weight percent of about 2.5 to about 5.5; a third binder has a weight percent of about 39.0 to about 53.0; and the nanoparticle-sized metal oxide has a weight percent of about 0.5 to about
 1. 